US9520574B2 - Electroluminescent devices based on phosphorescent iridium and related group VIII metal multicyclic compounds - Google Patents

Electroluminescent devices based on phosphorescent iridium and related group VIII metal multicyclic compounds Download PDF

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US9520574B2
US9520574B2 US13/643,054 US201113643054A US9520574B2 US 9520574 B2 US9520574 B2 US 9520574B2 US 201113643054 A US201113643054 A US 201113643054A US 9520574 B2 US9520574 B2 US 9520574B2
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Michelle Groarke
Kazunori Ueno
Mark Bown
Sven Andresen
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Commonwealth Scientific and Industrial Research Organization CSIRO
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Definitions

  • the present invention relates to novel phosphorescent materials, and to electroluminescent devices containing them.
  • An organic electroluminescent device is generally comprised of a pair of electrodes forming an anode and a cathode, and one layer or multiple layers comprising a hole transporting layer, emission layer (with an emissive material) and electron transporting layer.
  • a hole transporting layer forming an anode and a cathode
  • emission layer with an emissive material
  • electron transporting layer Into the organic layer(s), holes and electrons are injected from the anode and the cathode, respectively, thus resulting in excitons within the emission material. When the excitons transition to the ground state, the emissive material emits light.
  • an organic electroluminescent device which comprised a layer of an aluminium quinolinol complex (as electron transporting and luminescent material) and a layer of a triphenylamine derivative (as a hole transporting material) resulted in luminescence of about 1,000 cd/m 2 under an application of a voltage of 10 V.
  • Examples of related U.S. Patents include U.S. Pat. Nos. 4,539,507; 4,720,432 and 4,885,211.
  • the luminescence of such devices may fall into one of two main categories—fluorescence and phosphorescence, based on whether the luminescent material is a fluorescent material or a phosphorescent material.
  • the mechanism through which the luminescence is obtained differs between these categories of materials.
  • the present invention provides a new range of phosphorescent materials.
  • the present invention also provides new organic electroluminescent devices containing such phosphorescent materials.
  • an organic electroluminescent device comprising:
  • the phosphorescent material can be used as an emission material in the organic electroluminescent device.
  • the phosphorescent material may form a layer of the device, or a component of a layer of the device.
  • the phosphorescent material may be present as a dopant within a host material, wherein the host material may be an electron transporting material or a hole transporting material or both.
  • the possible substituents in rings A and B of the phosphorescent material used in the device may independently be selected from the group consisting of:
  • an organic electroluminescent device comprising:
  • a phosphorescent material comprising a complex of a metal atom M selected from Ir, Pt, Rh, Pd, Ru and Os and at least one ligand L, wherein the ligand L is represented by formula (1), as defined above.
  • a phosphorescent material of formula (2) ML m L′ n (2) wherein: M is a metal atom selected from Ir, Pt, Rh, Pd, Ru and Os, L is a ligand represented by formula (1), as defined above, L′ is a bidentate ligand of a different identity to L, m is an integer selected from 1, 2 and 3, and n is an integer selected from 0, 1 and 2.
  • a method for the production of a phosphorescent material comprising:
  • an organic electroluminescent device comprising the phosphorescent material of the third or fourth aspect.
  • a phosphorescent material of the third or fourth aspect in an organic electroluminescent device.
  • a phosphorescent material of the third or fourth aspect as an emission material in an organic electroluminescent device.
  • FIG. 1 is a schematic illustration of the basic structure of an organic electroluminescent device according to a first embodiment of the invention.
  • FIG. 2 is a schematic illustration of the basic structure of an organic electroluminescent device according to a second embodiment of the invention.
  • FIG. 3 is a schematic illustration of the basic structure of an organic electroluminescent device according to a third embodiment of the invention.
  • FIG. 4 is a schematic illustration of the basic structure of an organic electroluminescent device according to a fourth embodiment of the invention.
  • FIG. 5 shows the emission spectrum of the compound exemplified below as 10 at room temperature.
  • the phosphorescent material for use in the organic electroluminescent device of the present application comprises a complex of a metal atom M selected from Ir, Pt, Rh, Pd, Ru, and Os and at least one ligand L of formula (1).
  • the phosphorescent material may, in some embodiments be homoleptic (i.e. containing the same ligands that fall within the scope of the ligand L represented by formula (1)).
  • the phosphorescent material may be heteroleptic (i.e. containing different ligands falling within the scope of the ligand L represented by formula (1), or containing at least one ligand falling within the scope of the ligand L represented by formula (1) and other ligands (e.g. bidentate ligands L′ having the formula (5), (6) or (7) set out below)).
  • heteroleptic i.e. containing different ligands falling within the scope of the ligand L represented by formula (1), or containing at least one ligand falling within the scope of the ligand L represented by formula (1) and other ligands (e.g. bidentate ligands L′ having the formula (5), (6) or (7) set out below)).
  • phosphorescent material in its broadest sense to refer to any chemical substance containing the required metal and ligand of formula (1), and extends to compounds, complexes, polymers, monomers and the like materials. It will be understood that some forms of the phosphorescent material are polymer forms.
  • the reference to the material being “phosphorescent” indicates that the material has the property of being capable of emitting light following excitation, through transitioning of the excitons to ground state. This is typically from a triplet exciton state.
  • the phosphorescent material may be referred to as a phosphorescent complex, or a phosphorescent organometallic complex.
  • the metal atom is Ir.
  • Such phosphorescent materials containing Ir as the metal atom may be referred to as phosphorescent iridium complexes.
  • iridium tends to form a hexa-coordinate complex with the subject ligands.
  • the ligand of formula (1) coordinates to the iridium at two coordination sites.
  • the phosphorescent material may comprise up to 3 ligands L of formula (1), or may comprise one or two ligands of formula (1), and one or more additional ligands.
  • the phosphorescent material may comprises 3 bidentate ligands, specifically between one and three ligands L of formula (1), and 0, 1 or 2 further ligands L′.
  • the phosphorescent material may be of formula (2): ML m L′ n (2) wherein M and L are as defined previously, L′ is a bidentate ligand of a different identity to L, m is an integer selected from 1, 2 and 3, and n is an integer selected from 0, 1 and 2.
  • the phosphorescent material may comprise 1 or 2 ligands L of formula (1), and 0 or 1 additional bidentate ligands.
  • m+n 2.
  • the ligand L represented by formula (1) contains an A ring which is a 5-membered aromatic or non-aromatic heterocycle containing at least one nitrogen atom, wherein the nitrogen atom can bind (or is bound) to the metal atom.
  • the other 4 atoms in the A ring may be selected from carbon (containing H or a substituent), nitrogen (optionally containing H or a substituent), oxygen and sulphur atoms.
  • rings containing N and C such as pyrazoles, pyrazolines, imidazoles, imidazolines, triazoles, tetrazoles;
  • rings containing N, C and O such as oxazoles oxazolines, oxadiazoles
  • rings containing N, C and S such as thiazoles, thiazolines, thiadiazoles
  • the 4 atoms other than the nitrogen atom illustrated in Formula (1) in the A ring are carbon or nitrogen, wherein the carbon atoms contain H or a substituent and the nitrogen atoms may contain H or a substituent.
  • Possible substituents on the atoms in the A ring can be selected from the group consisting of:
  • the ligand L represented by formula (1) contains a B ring which is a 5-membered or 6-membered aromatic or non-aromatic carbocycle or heterocycle containing a carbon atom which is (or can be) bound to the metal atom (as illustrated in formula (1)).
  • the other 4 or 5 atoms in the B ring are selected from carbon (containing H or a substituent), nitrogen (which may be substituted or unsubstituted), oxygen and sulphur atoms.
  • the B ring may be selected from the group consisting of: rings containing only C, such as: benzene, cyclohexene, cyclohexadiene, cyclopentene and cyclopentadiene;
  • rings containing N and C such as: pyridine, pyridazines, pyrimidines, pyrroles, pyrazoles, dihydropyridines, dihydropridazines, dihydropyrimidines, pyrroline, pyrazolines;
  • rings containing O and C such as: pyranes, dioxins, furanes, dihydropyranes, dihydrofuranes;
  • rings containing S and C such as: thiophenes, dihydrothiophenes;
  • rings containing N, C and O such as: oxazines, oxazoles, dihydrooxazines;
  • rings containing S, C and O such as: oxathiazines, dihydrooxathiazine;
  • rings containing N, C and S such as: thiazoles;
  • ring B Some possible ring structures for ring B are illustrated by, but not restricted to, the examples below:
  • the 4 or 5 atoms other than the illustrated carbon atom in the B ring are each carbon, nitrogen or sulphur.
  • Possible substituents on the atoms in the B ring can be selected from the group consisting of:
  • Rings A and B are joined by a direct covalent bond as represented in formula (1).
  • Rings A and B are also joined via a tether Q.
  • Q is a linear, branched or cyclic alkyl, aryl or alkyl-aryl tether of between 3 and 20 carbon atoms in length, wherein:
  • Suitable tethers Q include, but are not restricted to, the following:
  • the tether is of at least 3 carbon atoms in length. When combined with the atoms from the A and B rings, this results in the formation of a minimum 7-membered ring.
  • a tether of 4 atoms in length (being carbon, or substitutes for carbon) forms an 8-membered ring, and so forth for increasing tether lengths.
  • the ligand L is of the formula (3):
  • Q and ring B are as defined previously, and wherein: A 1 and A 2 are each independently selected from the group consisting of: C, N, O and S, wherein the C or N may be substituted or unsubstituted, A 3 and A 4 are selected from the group consisting of: C and N, wherein the C may be substituted or unsubstituted.
  • the ligand L is of formula (4):
  • a 1 and A 2 are each independently selected from the group consisting of: C, N, O and S, wherein the C or N may be substituted or unsubstituted
  • a 3 and A 4 are selected from the group consisting of: C and N, wherein the C may be substituted or unsubstituted
  • B 1 and B 2 are each independently selected from the group consisting of: C, N, O and S, wherein the C or N may be substituted or unsubstituted
  • B 3 when present, is selected from the group consisting of: C, N, O and S, wherein the C or N may be substituted or unsubstituted
  • B 4 is selected from the group consisting of: C and N, wherein the C may be substituted or unsubstituted
  • B 5 is C.
  • a 1 and A 2 are C or N, wherein the C or N is unsubstituted or substituted.
  • B 1 , B 2 and B 3 are selected from C, N or S, wherein the C or N is unsubstituted or substituted.
  • Suitable ligands L include, but are not restricted to, the following:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 can be independently selected from the group consisting of:
  • any ligands known in the art may be used as the further ligands that may be complexed with the metal atom, when the number of ligands L of formula (1) are not sufficient to fill all co-ordination sites for the metal atom.
  • These may be monodentate, or multidentate, such as bidentate, tridentate, tetradentate or so forth. Bidentate ligands are preferred.
  • the further ligands L′ are bidentate.
  • Some examples are those of formulae (5), (6) and (7) set out below:
  • G is a ligand component comprising one or two substituted or unsubstituted carbon atoms, which is connected covalently to two O-atoms, and the O atoms can each bind to the metal M at the asterisk (*).
  • Each of Y and Y′, for each of formulae (5) and (6), are independently selected from 5-, 6- or 7-membered heterocycles which are unsubstituted or substituted by one or more substituents.
  • Y and Y′ contain at least one nitrogen atom as represented in formula (5) and formula (6).
  • the other 4, 5 or 6 atoms in the Y and Y′ rings are selected from carbon (containing H or a substituent), nitrogen (which may be substituted or unsubstituted), oxygen, sulphur and silicon (which may be substituted or unsubstituted) atoms.
  • the Y and Y′ rings (which contain at least one nitrogen atom) may be selected from the group consisting of:
  • rings containing N and C such as: pyrazoles, pyrazolines, imidazoles, imidazolines, triazoles, tetrazoles, pyrrolidines, pyrrolines, pyrrols, imidazolidines, pyrazolidines, piperidines, pyridines, dihydropyridines, pipirazines, dihydropyrazines, pyrazines, pyridazines, dihydropyridazines, dihydropyrimidines, pyrimidines, dihydrotriazines, triazines, azepines, dihydroazepines, tetrahydroazepines, azepanes, diazepines, dihydrodiazepines, tetrahydrodiazepanes, diazepanes; rings containing N, C and O, such as: oxazoles oxazolines, oxadiazoles, dioxazoles, o
  • Examples of 5- 6- and 7-membered carbocycles or heterocycles include: rings containing C, such as: benzenes;
  • rings containing N and C such as: pyrrolidines, pyrrolines, pyrrols, imidazolidines, imidazolines, imidazoles, pyrazolidines, pyrazolines, pyrazoles, triazoles, tetrazoles, piperidines, pyridines, dihydropyridines, pipirazines, dihydropyrazines, pyrazines, pyridazines, dihydropyridazines, dihydropyrimidines, pyrimidines, dihydrotriazines, triazines, azepines, dihydroazepines, tetrahydroazepines, azepanes, diazepines, dihydrodiazepines, tetrahydrodiazepanes, diazepanes; rings containing N, C and O, such as: oxazolines, oxazoles, oxadiazoles, dioxazoles,
  • Z is a ligand component connected via a covalent bond to ring Y, and connected to the metal atom via X.
  • ligand component Z refers to any group or moiety that may be located between ring Y and the atom X through which the ligand is attached to the metal atom.
  • the ligand component may be selected from:
  • a linear, branched or cyclic alkyl, aryl or alkyl-aryl group of between 1 and 20 carbon atoms in length wherein: one or more of the carbon atoms in the ligand component may by replaced with —O—, —S—, —CO—, —CO 2 —, —CH ⁇ CH—, —C ⁇ C—, —NH—, —CONH—, —C ⁇ N—, —Si— and —B— (wherein the —Si— and —B— contain substituents based on their valency), and wherein any carbon, nitrogen, silicon or boron atom of the ligand component may contain one or more substituents selected from the group consisting of halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sul
  • Examples of 5- 6- and 7-membered carbocycles or heterocycles include:
  • rings containing C such as: benzenes
  • rings containing N and C such as: pyrrolidines, pyrrolines, pyrrols, imidazolidines, imidazolines, imidazoles, pyrazolidines, pyrazolines, pyrazoles, triazoles, tetrazoles, piperidines, pyridines, dihydropyridines, pipirazines, dihydropyrazines, pyrazines, pyridazines, dihydropyridazines, dihydropyrimidines, pyrimidines, dihydrotriazines, triazines, azepines, dihydroazepines, tetrahydroazepines, azepanes, diazepines, dihydrodiazepines, tetrahydrodiazepanes, diazepanes; rings containing N, C and O, such as: oxazolines, oxazoles, oxadiazoles, dioxazoles,
  • X is selected from: N, O, S or P atoms. X forms a monovalent bond with the metal M at the asterisk (*).
  • the N and P atoms may contain one or more substituents selected from the group consisting of: alkyl, aryl, alkyl-aryl (wherein one or more of the carbon atoms in the alkyl, aryl, alkyl-aryl may be replaced with N, O, S, P or Si, said replacement atoms containing H or another substituent as required given the valency of the atom), halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, alkenyl, alkynyl or silyl.
  • substituents selected from the group consisting of: alkyl, aryl, alkyl-aryl (wherein one or more of the carbon atoms in the alkyl, aryl, alkyl-aryl may be replaced with
  • G is a ligand component comprising one or two substituted or unsubstituted carbon atoms and may additionally form part of a fused ring system.
  • Suitable substituents include: alkyl, aryl, alkenyl, heteroaryl, halogen, cyano, amide, imine, imide, amidine, amine, nitro, hydroxy, ether, carbonyl, carboxy, carbonate, carbamate, phosphine, phosphate, phosphonate, sulphide, sulphone, sulphoxide, alkynyl, silyl and substituents containing a functional group that can be polymerised or a polymer chain.
  • two substituents may together form a ring or fused ring system.
  • G is covalently connected to two O atoms via a single or double bond.
  • ligands L′ of formula (5), (6) and (7) include the following:
  • the phosphorescent material of one embodiment of the invention is of formula (2): ML m L′ n (2) wherein:
  • G is a ligand component comprising one or two substituted or unsubstituted carbon atoms, which is connected covalently to two O-atoms; and the O-atoms are each bound to the metal at the asterisk (*),
  • the phosphorescent materials of the present invention can be prepared by using synthetic procedures such as those described for example in:
  • the phosphorescent materials can be simply prepared by:
  • a precursor complex of Ir (as the metal), the precursor complex comprising substitutable ligands (in this case, 3 CH 3 COCHCOCH 3 ligands) is reacted with 3 molar equivalents of ligand L to produce Ir(L) 3 .
  • substitutable ligands in this case, 3 CH 3 COCHCOCH 3 ligands
  • a precursor complex of Ir comprising substitutable ligands (in this case, the complex is IrCl 3 .3H 2 O, and the ligands are —Cl and H 2 O) is reacted with 2 molar equivalents of ligand L to produce [IrL 2 Cl] 2 , and this product is reacted with another molar equivalent of ligand L to produce IrL 3 .
  • a precursor complex of Ir comprising substitutable ligands (in this case, the complex is IrCl 3 .3H 2 O, and the ligands are —Cl and H 2 O) is reacted with 2 molar equivalents of ligand L to produce [Ir(L) 2 Cl] 2 , and this product is reacted with one molar equivalent of ligand L′ to produce IrL 2 L′.
  • a precursor complex of Ir in the +1 oxidation state with substitutable ligands e.g. alkene ligands in a ⁇ 2 hapticity, in this case 1,5-cyclooctadiene
  • substitutable ligands e.g. alkene ligands in a ⁇ 2 hapticity, in this case 1,5-cyclooctadiene
  • heterocycle is well understood in the art of chemistry, and is used to refer to any cyclic groups having between one and five rings, and between 3 to 50 (preferably 5 to 20) ring atoms, of which at least one atom is a heteroatom.
  • the heterocyclic group is specifically a 5-membered, 6-membered or 7-membered heterocyclic group (a single-ring heterocyclic group), however the optional substituents for these groups may form a second ring that is fused to the main heterocyclic ring.
  • the heteroatoms may be selected from one or more of O, N, S, Si and P.
  • heterocyclic groups are the heteroaromatic (or heteroaryl) groups, which are aromatic groups containing one or more heteroatoms selected from one or more of O, N and S. Such heteroaromatic groups also fall within the definition of aryl group.
  • heteroaromatic groups which may constitute certain moieties in the phosphorescent material are outlined above.
  • heterocyclic groups include moieties of imidazole, benzimidazole, pyrrole, furan, thiophene, benzothiophene, oxadiazoline, indoline, carbazole, pyridine, quinoline, isoquinoline, benzoquinone, pyrazoline, imidazolidine, piperidine, etc.
  • cyclic is used in its broadest sense to refer to cyclic groups and linked or fused ring systems having between 3 and 50 ring atoms, which may be carbocyclic (containing carbon ring-atoms only) or heterocyclic (containing carbon atoms and at least one heteroatom), and may be saturated or unsaturated.
  • the number of rings is suitably between 1 and 5, preferably 1 or 2. In the case of 5-, 6- and 7-membered cyclic groups, these are single rings containing 5, 6 or 7 ring atoms.
  • the cyclic group is a carbocycle, that is, a ring containing carbon atoms as the ring atoms. In other instances where the number of ring atoms is not identified, the cyclic group may contain a single ring of any suitable number of ring atoms, or up to 5 linked or fused rings each containing any suitable number of ring atoms.
  • alkyl refers to linear or branched alkyl groups or cyclic alkyl groups, comprising between 1 and 20 carbon atoms. These are derived from alkanes. Examples of linear alkyl groups include methyl, propyl or decyl, and examples of branched alkyl groups include iso-butyl, tert-butyl or 3-methyl-hexyl. Examples of cyclic alkyl groups include cyclohexyl and fused alkyl cyclic ring systems.
  • aryl or “aryl group” is well understood in the art of chemistry, and is used to refer to any aromatic substituent.
  • the aromatic substituent preferably contains from 1 aromatic ring, up to 4 fused aromatic rings, and between 5 and 50 ring atoms.
  • the aryl group may be carbocyclic (i.e. contain carbon and hydrogen only) or may be heteroaromatic (i.e. contain carbon, hydrogen, and at least one heteroatom).
  • the aryl group may be monocyclic such as a phenyl, or a polycyclic aryl group such as naphthyl or anthryl.
  • aryl groups include a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, pyrenyl group, etc.
  • aryl is also used to describe an aromatic ring with any degree of substitution.
  • alkyl-aryl refers to a group containing an alkyl group connected to an aryl group.
  • tether refers to a chain that joins two groups together, such as the two rings A and B.
  • halogen refers to fluorine, chlorine, bromine and iodine.
  • amide refers to substituents containing the group —C(O)NRR′, wherein R and R′ are selected from H, alkyl, aryl or alkyl-aryl groups, which have been defined previously.
  • imide refers to substituents containing the group —C(O)NRC(O)R′, wherein R and R′ are selected from H, alkyl, aryl or alkyl-aryl groups.
  • mine refers to substituents containing the group —C( ⁇ NR)R′, wherein R and R′ are selected from H, alkyl, aryl or alkyl-aryl groups.
  • amidine refers to substituents containing the group —C( ⁇ NR)NR′R′′, wherein R, R′ and R′′ are selected from H, alkyl, aryl or alkyl-aryl groups.
  • amine refers to the amino group —NH 2 , and also to secondary and tertiary alkylamino, arylamino and alkylarylamino groups.
  • arylamino group include a diphenylamino group, ditolylamino group, isopropyldiphenylamino group, t-butyldiphenylamino group, diisopropyldiphenylamino group, di-t-butyldiphenylamino group, dinaphthylamino group, naphthylphenylamino group, etc.
  • alkylamino group include dimethylamino group, diethylamino group, dihexylamino group, etc.
  • Niro refers to —NO 2 .
  • Cyano refers to —C ⁇ N.
  • Hydroxy refers to —OH.
  • “Ether” refers to groups containing an ether group R—O—R′, wherein R and R′ are selected from H, alkyl, aryl or alkyl-aryl groups, which have been defined previously.
  • Carbonyl refers to substituents containing a carbonyl group —C ⁇ O.
  • groups include ketones (—COR), aldehydes (—CHO), carboxylic acids (—CO 2 H), enones (—C ⁇ O—CR ⁇ CR′R′′), esters (—CO 2 R), acyl halides (—COhalogen), acid anhydrides (—C( ⁇ O)—O—C( ⁇ O)—R′) and carbonates R—O—C( ⁇ O)—O—R′ as examples, where each of R, R′ and R′′ is an alkyl or aryl group.
  • Carboxyl refers to substituents containing a carboxylate group (RCO 2 ⁇ ), where R is alkyl or aryl, as examples.
  • “Carbamate” refers to substituents containing a carbamate group —O—C( ⁇ O)—NRR′, where R and R are typically alkyl or aryl, or may together form a ring.
  • Phosphine refers to —PR 2 , wherein R is selected from H, alkyl, aryl or alkyl-aryl. “Phosphate” refers to substituents containing the PO 4 group, with any suitable end groups such as H, aryl and/or alkyl. Examples include —OP( ⁇ O)—(OR) 2 , where each R is independently H, alkyl, aryl, etc. “Phosphonate” refers to a moiety derived from the removal of an atom from a phosphonate of the formula O ⁇ P(OR) 2 R′.
  • “Sulphide” refers to —SR where R is H, alkyl or aryl, as an example.
  • “Sulphone” refers to groups containing the unit —S( ⁇ O) 2 —, such as —S( ⁇ O) 2 —R where R is alkyl or aryl, as examples.
  • “Sulphoxide” refers to groups containing the unit —S( ⁇ O)—, such as —S( ⁇ O)—R where R is alkyl or aryl, as examples.
  • Alkenyl refers to hydrocarbon chains of between 2 and 20 carbon atoms in length containing at least one —C ⁇ C— group. Examples include vinyl, allyl (including substituted variants thereof) and all isomers of propenyl, butenyl, heptenyl, hexenyl, etc.
  • Alkynyl refers to hydrocarbon chains of between 2 and 20 carbon atoms in length containing at least one —C ⁇ C— group. Examples include propynyl, butynyl, heptynyl, hexynyl, etc.
  • “Silyl” refers to a moiety of the formula —SiR 3 (wherein R is any substituent, such as H, alkyl, aryl, etc), and silyl ethers —SiR′ 2 OR′′ where R′ and R′′ are any suitable substituents such as alkyl, aryl, and alkyl-aryl, etc. Further examples include a trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, methyldiphenylsilyl group, dimethylphenylsilyl group, triphenylsilyl group, etc.
  • the ligand may contain a substituent which contains a functional group that can be polymerised or a polymer chain.
  • the functional group or polymer chain may be attached via any suitable divalent linking group, which may be referred to as —R linker -.
  • divalent linking groups include —O—, —NH—, —Nalkyl-, —Naryl-, -alkyl- (such as —(CH 2 ) x —), —CO 2 —, —CO—, -aryl-, -heteroaryl-, and combinations thereof.
  • Combinations include, as examples, —O-aryl-, —NH-aryl-, —Nalkyl-aryl-, —(CH 2 ) x -aryl-.
  • Functional groups that can be polymerised include —R linker -′CR 1 ⁇ CHR 2 , where R linker is as defined above, R 1 is hydrogen, alkyl, aryl or heteroaryl, and R 2 is hydrogen, a halogen atom, nitro group, acetyl group, acrylate group, amide group, cyano group, carboxylate group, sulphonate group, an aryl, an alkyl or a heterocyclic group. Each of these substituents may be further substituted by one or more further substituents selected from the range of possible substituents for A rings identified previously. The point of attachment of the monomer segment is via the carbon atom marked ′C.
  • the monomer may be polymerised subsequently to form a polymeric version of the phosphorescent material.
  • Other examples of functional groups that can be polymerised include amino acids, lactams, hydroxy acids, lactones, aryl halides, boronic acids, alkynes, epoxides and phosphodiesters.
  • the ring may be a single ring of between 5 and 20 atoms in size, in which the ring is carbocyclic or heterocyclic (i.e. the atoms are selected from carbon and heteroatoms), or a fused ring system of between 5 and 50 atoms in size, and containing from 2 to 4 rings.
  • the fused ring system may also be fused to other rings of the subject compound—such as the A or B ring in the case of ligands L of formula (1). Examples of suitable rings and fused rings include those described above in the context of cyclic.
  • the phosphorescent materials of the present invention can be used to fabricate organic electroluminescent devices which can be tuned to produce an emission colour from 400-800 nm.
  • the invention provides an organic electroluminescent device comprising:
  • organic compound layer or one or more of the organic compound layers, comprises a phosphorescent material as described above.
  • the organic electroluminescent device according to the present invention is composed of organic compounds layer(s) aligned between an anode and a cathode.
  • the organic layer(s) may be constituted by:
  • the organic compound layer comprising the above-mentioned phosphorescent material of the present application may be formed separately, or together, with the other layers (if any other layers are present) between the pair of electrodes (cathode and anode).
  • Suitable formation techniques include vacuum deposition or solution process.
  • the thickness of the organic compound layer may be preferably less than at most 10 ⁇ m, more preferably less than 0.5 ⁇ m, even more preferably 0.001-0.5 ⁇ m.
  • the organic electroluminescent device of embodiments of the present application may have a single layer structure comprised only of the compound as defined by formula (1) as shown in FIG. 1 or be a multiple layered structure of two or more layers as shown in FIGS. 2, 3 and 4 .
  • FIG. 1 is a schematic cross section of a first embodiment of the organic electroluminescent device of the present invention.
  • the organic electroluminescent device includes a substrate 1 , an anode 2 (deposited on the substrate 1 ), an emission layer 3 (deposited on the anode 2 ) and a cathode 4 (deposited on the emission layer 3 ).
  • the emission layer 3 forms a single organic compound type-layer.
  • This single layer may be composed entirely of a compound having hole transporting ability, electron transporting ability and luminescence ability (associated with the re-combination of electrons and holes) based on its own properties, or through combination of the properties of that material with a host or dopant.
  • the phosphorescent material of the present application can serve as a dopant.
  • the phosphorescent material of the present application can function as a hole or electron transporting layer.
  • the emission layer 3 may preferably have a thickness of 5 nm to 1 ⁇ m, more preferably 5 to 50 nm.
  • FIG. 2 shows another embodiment of the organic electroluminescent device of the present invention in the form of a multiple layer-type device including a hole transporting layer 5 and an electron transporting layer 6 .
  • the organic electroluminescent device includes a substrate 1 and an anode 2 (deposited on the substrate 1 ).
  • the hole transporting layer 5 is deposited on the anode 2 .
  • the electron transporting layer 6 is deposited on the hole transporting layer 5 , and a cathode 4 is deposited on the electron transporting layer 6 .
  • the hole transporting layer 5 and the electron transporting layer 6 may contain the phosphorescent material of the present application as a dopant(s) for forming a emission layer 3 .
  • each of the hole transporting layer 5 and the electron transporting layer 6 may have the thickness of 5 nm to 1 ⁇ m, more preferably 5 nm to 50 nm
  • FIG. 3 shows another embodiment of the organic electroluminescent device of the present invention in the form of a multiple layer-type device comprising a hole transporting layer 5 , an emission layer 3 and an electron transporting layer 6 .
  • the organic electroluminescent device includes a substrate 1 , an anode 2 (deposited on the substrate 1 ), a hole transporting layer 5 (deposited on the anode 2 ), an emission layer 3 (deposited on the hole transporting layer 5 ), an electron transporting layer 6 (deposited on the emission layer 3 ) and a cathode 4 (deposited on the electron transporting layer 6 ).
  • each of the hole transporting layer 5 , the emission layer 3 and the electron transporting layer 6 may be formed by use of a hole transporting compound, an emissive compound and an electron transporting compound, respectively or as a mixture of these kinds of compounds.
  • the phosphorescent material of the present application can form the emission layer 3 , or be a component (such as a dopant) of the hole transporting layer 5 , or be a component (such as a dopant) of the electron transporting layer 6 .
  • FIG. 4 shows another embodiment of the organic electroluminescent device of the present invention with multiple layers comprising a hole injection layer 7 , a hole transporting layer 5 , an emission layer 3 and an electron transporting layer 6 .
  • the organic electroluminescent device includes a substrate 1 , an anode 2 (deposited on the substrate 1 ), a hole injection layer 7 (deposited on the anode 2 ), a hole transporting layer 5 (deposited on the hole injection layer 7 ), an emission layer 3 (deposited on the hole transporting layer 5 ), an electron transporting layer 6 (deposited on the emission layer 3 ) and a cathode 4 (deposited on the electron transporting layer 6 ).
  • each of the hole injection layer 7 , the hole transporting layer 5 , the emission layer 3 and the electron transporting layer 6 may be formed by use of a hole injection compound, a hole transporting compound, an emissive compound and an electron transporting compound, respectively, or as a mixture of these kinds of compounds.
  • the phosphorescent material of the present application can form the emission layer, or be a component (such as a dopant) in the hole transporting layer 5 or the electron transporting layer 6 .
  • each layer may be formed by either vacuum deposition or wet process using low molecular weight or polymer compounds or a mixture of low molecular weight and polymer compounds.
  • Each thickness of the layer 3 , 5 and 6 may preferably range from 1 nm to 1 ⁇ m.
  • Each of the thickness of the cathode and the anode may be preferably 100-200 nm
  • the organic layer structures in the devices shown in FIGS. 1, 2, 3 and 4 represent the basic structure, respectively, so that the structure may be appropriately optimized depending on characteristics demanded. Examples of suitable modifications include the incorporation of one or more additional layers.
  • the hole transporting layer may be altered to comprise a hole injection layer (deposited on the anode) and hole transporting layer (deposited on the hole injection layer).
  • FIGS. 1, 2, 3 and 4 More specific embodiments of the device structure other than those of FIGS. 1, 2, 3 and 4 are shown below, but not restricted to these device structures.
  • the phosphorescent material of the present application may be formed as an emission layer, or as a dopant in a hole transport layer or an electron transport layer. According to some embodiments, there is provided the use of the phosphorescent material of the present application as an emission material in an organic electroluminescence device, or as a dopant in a hole transport layer, or as a dopant in an electron transporting layer.
  • the phosphorescent material of the present application may be used in combination with one or more of a hole injection material, a hole transporting compound (or material), an electron transporting compound and/or an additional emission compound, examples of which may include the following:
  • Exemplary hole transporting materials/compounds include:
  • Exemplary electron transporting materials/compounds include:
  • anode As a material for the anode (e.g. 2 in the Figures), it is preferred to use one having a large work function, examples of which may include metals, such as gold, platinum, nickel, palladium, cobalt, selenium, vanadium and their alloys; metal oxides, such as tin oxide, zinc oxide, indium zinc oxide (IZO) and indium tin oxide (ITO) and electroconductive polymers, such as PEDOT:PSS, polyaniline, polypyrrole and polythiophene and derivatives thereof. These compounds may be used singly or in combination of two or more species.
  • metals such as gold, platinum, nickel, palladium, cobalt, selenium, vanadium and their alloys
  • metal oxides such as tin oxide, zinc oxide, indium zinc oxide (IZO) and indium tin oxide (ITO)
  • electroconductive polymers such as PEDOT:PSS, polyaniline, polypyrrole and polythiophene and derivatives thereof.
  • the cathode As a material for the cathode (e.g. 4 in the Figures), it is preferred to use one having a smaller work function, usually under 4.0 eV, examples of which may include; metals such as sodium, magnesium, calcium, lithium, potassium, aluminium, indium, silver, lead, chromium and their alloys, or oxides.
  • metals such as sodium, magnesium, calcium, lithium, potassium, aluminium, indium, silver, lead, chromium and their alloys, or oxides.
  • the charge blocking layer may be deposited adjacent to either electrode to avoid current leakage as mentioned in embodiments (3) to (8).
  • the charge blocking material it is preferred to use an inorganic compound, examples of which may include aluminium oxide, lithium fluoride, lithium oxide, caesium oxide, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, aluminium nitride, titanium oxide, silicon oxide, silicon nitride, boron nitride, vanadium oxide.
  • the substrate (e.g., 1 shown in the Figures) for the organic electroluminescence device of the present invention may include an opaque substrate made from any suitable material, such as metal or ceramics, or a transparent substrate made from any suitable transparent material such as glass, quartz, plastics, etc.
  • the devices of the present application can be provided in the form of a stacked organic electroluminescent (EL) device.
  • EL organic electroluminescent
  • the present application also extends to electronic devices comprising the organic electroluminescent device of the present invention, including displays and light sources.
  • the crude pyrazole (5 g, 24.7 mmol) was taken up in DMF (25 mL) and iodomethane (2.3 ml, 37.1 mmol) and K 2 CO 3 (5.1 g, 37.1 mmol) were added.
  • the reaction mixture was heated at an oil bath temperature of 100° C. for 1 hour.
  • the reaction was then cooled to room temperature, diluted with water (100 mL) and extracted with EtOAc (50 mL).
  • the organic phase was then washed twice with water (2 ⁇ 100 mL), dried over MgSO 4 and the solvent was evaporated.
  • the crude product was obtained as a 6:1 mixture of regioisomers (by 1 H NMR).
  • the organic phase was washed with water (100 mL) and dried over MgSO 4 .
  • the solvent was evaporated to give the crude N—H-pyrazole which was used without further purification.
  • the N—H-pyrazole was taken up in EtOH and hydrazine hydrate (2.5 mL, 50.1 mmol) was added. The reaction was allowed to stir at an oil bath temperature of 80° C. for 1 hour and then cooled to room temperature and the solvent was evaporated. The crude pyrazole was isolated and used without further purification.
  • Ligand 1 may alternatively be reacted with other metal reagents derived from Pt, Rh, Pd, Ru or Os.
  • Ligand 2 may alternatively be reacted with other metal reagents derived from Pt, Rh, Pd, Ru or Os.
  • the pyrazole 3 (1 g, 3.76 mmol) and iridium(III) chloride (0.571 g, 1.71 mmol) were combined in ethoxyethanol (10 ml)/water (3 ml) and degassed.
  • the reaction mixture was heated under an atmosphere of N 2 at an oil bath temperature of 130° C. for 4 hours.
  • the reaction was then allowed to cool to room temperature and concentrated.
  • the crude reaction residue was taken up in CH 2 Cl 2 and washed with water, saturated aqueous NaHCO 3 and brine, dried over MgSO 4 and the solvent was evaporated.
  • the crude product was treated with Et 2 O and the yellow precipitate was filtered. Dimer 6 (1 g, 77% yield) was used without further purification.
  • Ligand 3 may alternatively be reacted with other metal reagents derived from Pt, Rh, Pd, Ru or Os.
  • Dimer 4 (100 mg, 0.08 mmol), picolinic acid (25 mg 0.20 mmol) and sodium carbonate (90 mg, 0.85 mmol) were taken up in 4 ml of 2-ethoxyethanol.
  • the mixture was degassed with N 2 and heated under an atmosphere of nitrogen at an oil bath temperature of 60° C. for one hour. After this time the reaction was complete as indicated by NMR analysis.
  • the solvent was removed under reduced pressure, CH 2 Cl 2 was added and the excess Na 2 CO 3 was filtered off. The remaining solution was reduced to half its volume, the product was precipitated into n-hexane and collected by filtration to give 76 mg (67%) of the desired heteroleptic complex 7.
  • Dimer 5 (1.19 g, 0.9 mmol), 2-(3-tert-butyl-1H-1,2,4-triazol-5-yl)pyridine (457 mg 2.26 mmol) and sodium carbonate (958 mg, 9 mmol) were dissolved in 159 ml 2-ethoxyethanol.
  • the mixture was degassed with N 2 and heated under an atmosphere of nitrogen at an oil bath temperature of 90° C. for ninety minutes. After this time the reaction was complete as indicated by NMR analysis. The solvent was removed under reduced pressure, CH 2 Cl 2 was added and the excess Na 2 CO 3 was filtered off.
  • Dimer 6 (50 mg, 0.033 mmol), 2-(3-tert-butyl-1H-1,2,4-triazol-5-yl)pyridine (17 mg. 0.082 mmol) and sodium carbonate (8.74 mg, 0.082 mmol) were taken up in 2-ethoxyethanol (10 mL) and heated under an atmosphere of nitrogen at an oil bath temperature of 80° C. for 90 minutes. The reaction mixture was allowed to cool to room temperature and the solvent was evaporated. The residue was diluted in CH 2 Cl 2 and filtered through a pad of celite. Purification of the crude product was carried out by chromatography on silica (4:1 EtOAc/Hexane as eluant) to give 50 mg of the desired product 9 (82% yield).
  • Dimer 5 150 mg, 0.11 mmol
  • 2-(3-tert-butyl-1H-1,2,4-triazol-5-yl)pyrazine 69 mg. 0.34 mmol
  • sodium carbonate 121 mg, 1.14 mmol
  • the mixture was degassed with N 2 and heated under an atmosphere of nitrogen at an oil bath temperature of 80° C. for ninety minutes. After this time the reaction was complete as indicated by NMR analysis. The solvent was removed under reduced pressure, CH 2 Cl 2 was added and the excess Na 2 CO 3 was filtered off.
  • Dimer 6 (50 mg, 0.03 mmol), tropolone (10 mg, 0.08 mmol) and sodium carbonate (8.74 mg, 0.08 mmol) were taken up in 2-ethoxyethanol (10 mL) and heated under an atmosphere of nitrogen at an oil bath temperature of 80° C. for 90 minutes. The reaction mixture was allowed to cool to room temperature and the solvent was evaporated. The residue was diluted in CH 2 Cl 2 and filtered through a pad of celite. The crude product was treated with methanol/water (10 mL, 9:1) and the brown precipitate was filtered to give the purified product 13 (50 mg, 72%).
  • Dimer 6 (100 mg, 0.06 mmol), methacrylic acid (14 ⁇ L, 0.16 mmol) and sodium carbonate (17 mg, 0.16 mmol) were taken up in ethanol/water (4:1, 5 mL) and heated under an atmosphere of nitrogen at an oil bath temperature of 90° C. for 90 minutes. The reaction mixture was allowed to cool to room temperature and the solvent was evaporated. The residue was diluted in CH 2 Cl 2 (20 mL) and washed with water (20 mL), saturated NaHCO 3 (20 mL) and dried over anhydrous MgSO 4 . The solvent was evaporated to give the desired product 14 (0.1 g, 75%) as a yellow solid.
  • Ligand 15 may be reacted with IrCl 3 to form a tris heteroleptic complex in a manner outlined in examples 4-14. Alternatively, Ligand 15 may be reacted with other metal reagents derived from Pt, Rh, Pd, Ru or Os.
  • Ligand 17 may be reacted with Ir to form a tris heteroleptic or homoleptic complex in a manner outlined in examples 4-16. Alternatively, Ligand 17 may be reacted with other metal reagents derived from Pt, Rh, Pd, Ru or Os.
  • 6-bromo-6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-one (239 mg, 1.0 mmol) and thioacetamide (100 mg, 1.3 mmol) were heated in DMF (10 ml) at an oil bath temperature of 80° C. for 33 hours. After this time the solution was cooled to room temperature and the solvent removed in vacuo. The crude residue was diluted with CH 2 Cl 2 (150 mL) and washed with saturated aqueous NaHCO 3 (50 mL) and water (2 ⁇ 50 mL), dried over MgSO 4 and the solvent evaporated to give a crude orange oil.
  • Ligand 18 may be reacted with Ir to form a tris heteroleptic or homoleptic complex in a manner outlined in examples 4-16. Alternatively, Ligand 18 may be reacted with other metal reagents derived from Pt, Rh, Pd, Ru or Os.
  • Ligand 19 may be reacted with Ir to form a tris heteroleptic or homoleptic complex in a manner outlined in examples 4-16. Alternatively, Ligand 19 may be reacted with other metal reagents derived from Pt, Rh, Pd, Ru or Os.
  • An ITO patterned glass substrate was successively sonicated in acetone and iso-propanol for 15 minutes and dried. Then PEDOT:PSS was spin coated on top of the ITO at a spin-speed of 4000 rpm for 1 min and baked on hot plate at 150° C. for 15 min. The thickness of the PEDOT:PSS layer was determined to be 40 nm. After this the substrate was transferred into a glove box and an emission layer was spin coated on top of the PEDOT:PSS layer at a spin-speed of 3000 rpm for 1 min and baked at 80° C. for 30 min. A solution consisting of PVK, PBD, TPD and compound 10, dissolved in chlorobenzene, was used to form the emission layer.
  • the weight ratio of the four components was 65:25:9:6.
  • the thickness of the emission layer was determined to be 90 nm.
  • layers of TPBi (hole blocking layer, 20 nm), LiF (electron injection layer, 1 nm) and Al (cathode, 120 nm) were subsequently deposited under a vacuum of 1 ⁇ 10 ⁇ 5 Pa.
  • the device When a voltage was applied between the anode and the cathode, the device emitted light with a maximum wavelength of 565 nm.
  • the CIE colour coordinates were (0.49; 0.49).
  • the maximum current efficiency was 20 cd/A at a brightness of 1800 cd/m 2 and a voltage of 15 V.
  • the maximum brightness was 20000 cd/m 2 at 21 V.

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